Synthesis of New Polymer Ionomers via Ring-Opening Metathesis Polymerization

The N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide (2a) and N-phenyl-exo-endo-nor-bornene-5,6-dicarboximide (2b) monomers were synthesized and polymerized via ring-opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine) benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II). Both catalysts were used to synthesize random and block high molecular weight copolymers which were further hydrogenated using a Wilkinson’s catalyst. Then, the saturated copolymers were modified by reacting with sodium 4-hydroxybenzene-sulfonate dihydrate to generate new ionomers with fluoro-sulfonic acid pendant groups.

New Azomethine Compounds on the Basis <i>m</i>-Phenylenediamine and Substituted Benzaldehydes Capable of Oxidative Polymerization

Low-temperature condensation of m-phenylene diamine and various aromatic aldehydes (benzaldehyde, m-, o-nitrobenzaldehyde, p-diethylaminobenzaldehyde, o-, p-hydroxybenzaldehyde and 4-hydroxy-3,5-ditert-butylbenzaldehyde) in the ethyl alcohol medium synthesized new azomethine compounds. With the help of spectral methods and elemental analysis, the structure of the azomethine compounds obtained was confirmed. It was founded that irradiation of azomethine compounds with UV light at a wavelength of 300 - 330 nm results in their emission. The luminescent properties of the resulting compounds are due to the presence of chromophore azomethine groups in the molecule structure. In particular, the π-electrons of the azomethine bonds can undergo irradiation to a different energy levels, accompanied by fluorescence. It was shown that synthesized azomethine compounds are capable of oxidative polymerization. Based on azomethine compounds in hydrochloric acid solution synthesized polymers with conjugated bonds, which had low molecular-mass characteristics. It is shown that the oxidative polymerization of azomethines proceeds through a slow (one-electron transfer) and rapid (recombination of the radical cations) stage.

Oxidative Polymerization of N-Phenylanthranilic Acid in the Heterophase System

Polymers of N-phenylanthranilic acid were obtained by oxidative polymerization in the heterophase system in the presence of chloroform. Effect of synthesis conditions on the chemical structure of the polymers was studied. It was found that the growth of polymeric chain occurs via C-C joining into 2- and 4-positions of phenyl rings with respect to nitrogen. Thermal stability of poly-N-phenylanthranilic acid was studied.

High-permeance crosslinked PTMSP thin-film composite membranes as supports for CO_2 selective layer formation

In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO_2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite(TFC) membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl)-1-propyne](PTMSP). This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the CO_2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine(PEI) and poly(ethyleneglycol) diglycidyl ether(PEGDGE) as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1-2.5 μm. The claimed membranes showed the following characteristics: CO_2 permeance is equal to 50—54 m^3(STP)/(m^2 h bar)(18,500—20,000 GPU), ideal CO_2/N_2 selectivity is 3.6-3.7, and their selective layers are insoluble in chloroform. Thus, the developed highpermeance TFC membranes are considered as a promising supports for further modification by enhanced CO_2 selective layer formation.

Carbcations Chemistry： β-Methyl Shift--A New Rearrangement of the Carbcations Bridged Alicyclic Hydrocarbons

Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of a new intramolecular rearrangement of the carbcations bridged alicyclic hydrocarbons--2,4-moving of the methyl groups （β-methyl shift）. The proof of realization of such rearrangement is direct and primary formation 1,4-dimethyladamantane from 1,2-dimethyladamatane, passing a formation stage of the thermodynamic much stable 1,3-dimethyladamantane; direct formation 1,3,6-trimethyladamantane from 1,3,4-trimethyladamantane, excepting a formation stage 1,3.5-trimethyladamantane, and also other isomers which formation is impossible to explain by means of known 1,2-methyl shift （a-methyl shift）.

, Optimization Studies on Synthesis of TKX-50

A systematic study of TKX-50 and ABTOX synthesis using both Klap6tke and Tselinskii modified procedures is described. The influence of temperature, moisture, acid amount and nature on the most critical synthesis step - diazidoglyoxime cyclization is shown. Experimental results show that presence of moisture in reaction mixture leads to product yield decreasing. The reaction temperature is another key parameter affecting product yield. High reaction temperature shows negative influence on the product yield in Klap6tke method. In Tselinskii procedure the yield of product grows with the reaction temperature increasing. For Klap6tke one-pot method, combination of N-methyl-2-pyrrolidone with 1,4-dioxane is the best solvent, whereas Tselinskii one-pot procedure gives high yield of product when combination of toluene with 0.5 equiv, of 1,8-diazabicyclo[5.4.0]undec-7-ene （DBU） is used. Us- ing optimized conditions one-pot five-step synthesis of TKX-50 starting from glyoxime is successfully performed and scaled up to 50 g.

Novel method for the preparation of Cs-containing FAU（Y） catalysts for aniline methylation

Cs-containing FAU（Y）-type zeolite catalysts were prepared by conventional and novel ion exchange procedures followed by incipient wetness impregnation with CsOH. The novel ion exchange procedure involved hydrothermal treatment of NaY zeolite in aqueous solution of CsCl at 140-200 ℃ for 6-24 h. The samples were characterized by low-temperature nitrogen adsorption, X-ray fluorescence analysis, X-ray powder diffraction, scanning electron microscopy, 23Na, 27Al and 133Cs magic angle spinning nuclear magnetic resonance, CO2 and NH3-Temperature programmed desorption. The results show that hydrothermal treatment at 200 ℃ allows to obtain higher degrees of ion-exchange （up to 83%） with respect to conventional method giving maximum 66%- 69%. Catalytic properties of Cs-containing FAU（Y） were studied in aniline methylation. The yield of Nomethylani- line is shown to correlate with catalyst＇s basicity. The best catalyst performance was achieved over the catalyst with the highest ion-exchange degree impregnated with CsOH. The selectivity to N-methylaniline over this catalyst reached 96.4%.

耦合膜系统实现从工业污水和卤水中有价物质提取

金砖五国,包括中国、俄罗斯、巴西、南非和印度,为世界经济高速发展的新兴经济体.在人口增长、环境保护、饮用水以及食品需求等方面存在共同问题.金砖五国社会发展分布呈现两极化,有人口高密度发达工业和农业地区,也有基础设施、电力和净水供应严重缺乏的偏远地区.我们面临与西方发达国家不同的挑战.生物工艺技术可能会有效地解决碳循环问题,化石燃料会逐渐被可再生能源替代,但是对于制约高科技和经济发展的稀有和贵重金属,一旦被开采并进入到生态圈,则很难再生且不可持续.最为典型的是电子器件、电池和太阳能电池板等的需求增长,大量的贵金属从地下资源流失到城市和工业生产过程.将这些资源重新回收是熵减小过程,需要耗费大量能源.

Perylene Diimide Incorporated Polyurethane Polymer as Potential Colour Filter Material with Non-fluorescent Property

A novel polyurethane polymer containing perylene diimide(PDI)unit and aniline segment,denoted as PU-PDI,was designed and synthesized.Their tensile property and photophysical characteristic were investigated using various experimental and theoretical techniques.It is found that the elongation of PU-PDIs can reach more than 1000%,indicating good tensile performance.Moreover,based on the photoinduced electron transfer mechanism,the aniline segments in polyurethane can quench the auto-fluorescence of PDI unit to a negligible value,which overcomes the intractable fluorescence drawbacks of conventional colour filters.The non-emissive characteristic,in combination with the good thermal stability and tensile property of PU-PDI,provides a feasible design strategy to fabricate optical filters with high display quality.